Fluorinated compound and method of producing same



Jan. 9, l2,186,916

P. J. wlEzEvlcl-l. Now BY JUDICIAL CHANGE oF NAME P. J. GAYLOR FLUORINATED COIPUUND AND METHOD 0F PRODUCING SAME Filed Jan. l1, 1954 kWisQ WY@ N QN :hm QM.: MW wN NNI.'

WUN OQLUNQ Q Q. QI WN pao v Patented Jan. 9, 1940 PATENT oFFlcE N K FLUORINATED COMPOUND AND METHOD F PRODUCING SAME Peter J. Wiezevich, Elizabeth, N. J., now by judicial change of name Peter J. Gaylor, asaignor to Standard Oil Development Company, a corporation of Delaware Application January 11, 1934, Serial No. 706,230

ciaims.

'Ihis invention deals with the preparation and use of relatively high boiling oils and solids containing fiuorine. It especially involves the production of fluoro derivatives boiling above 200 C.

In the drawing is shown in diagrammatic form an apparatus for producing fluorine-containing oils.

Heretofore chlorine derivatives have been used to a large extent for various purposes, as for example. non-inammable inpregnating agents, plasticizers, etc., without very much success. This is due mainly to the fact that aliphatic chlorine compounds are too unstable, especially in the presence of moisture and metals, giving oil hydrochloric acid very readily, and often polymerizing to dark colored heavy products. The pure aromatic chloro derivatives, such as chlorinated diphenyls or naphthalenes, have been foundtobe quite stable at ordinary temperatures, but one of the main objections of such compounds is the fact that the chlorine ailects the boiling point too markedly, so that if,.for example, a really noniniiammable material is desired, the amount of chlorine required to give this eilect wouldproduce only solid products having very limited uses.

Fluorine compounds are much more stable than the corresponding chlorine derivatives, making it possible to utilize aliphatic compounds for purposes hitherto considered impractical with chlorinated products. Furthermore, in the case of aromatic hydrocarbons, for a given boiling point of the product, it is possible to introduce a considerably higher percentage of iiuorine than chlorine, giving a much wider range of liquid and solid non-inflammable compounds for selection. Other advantages will be apparent from the subsequent description.

As raw materials for this process I employ organic substances, generally those capable of giving iiuoro derivatives boiling above 400" F. and preferably those organic compounds boiling above 400 F. Such compounds as petroleum distillates, as for example kerosene, gas oil, lubricating oil, fuel oil, or cracking coil tar fractions, extracts of petroleum or its fractions obtained with solvents such as SO2, phenol, nitrobenzene, furfuroi, cresci and other similar agents, treated oils, as white or refined oils, propane treated oils, hydrogenated or hydroned oils, products of carbonization of mineral oils, coal, lignite, and the like, animal, vegetable, and iish oils and other glycerides, high boiling esters Lsuch as dibutyl phthalate, tricresyl phosphate, chlorinated esters, and other esters as those described in my U. S. ;5 Patent 2,104,408. Other compounds which may be so treated are chlorinated4 petroleum products,

oxidation products of oils and waxes, sulfur containing compounds, high boiling alcohols, acids, ketones, amines, amides, aldehydes, ethers, hetervocyclic compounds such as pyridine, thiopene, etc., aromatic compounds or coal tar products as naphthalene, diphenyl, benzene, toluene, xylene, diphenyl oxide, diphenylene oxide, and the like, chlorinated compounds such as chlorinated or brominated wax, chlorinated naphthalene, dichlorethyl ether, Chlor-diphenyl, brombenzene, nitro compounds such as nitrobenzene, hexyl nitrate, cyclic compounds such as cyclohexane, tetralin, hexalin, dioxan, and the like, phenols, aniline and similar compounds, polymers such as polymerized isobutylene of 1,000. to 10,000 molecular weight, polystyrene, polyindene, polyvinyl acetylene, polychlorprene, and other polyvinyl compounds, or oxygenated polymers such as those described in my U. S. Patent 2,123,641, as well as hydro rubber, rubber, chlorinated rubber, wax, petrolatum, thickened glycerides or voltolized mineral or glyceride oils, or stabilized esters such as those mentioned in U. S. Patent 2,107,316 in the names of Peter J. Wiezevich and Luther B. Turner, aromatic materials similar to those described in my U. S. Patent 2,079,783, cellulose esters and ethers, resins such as the Bakelite, coumarone, and other types, rosin, shellac, plastics, products obtained by the action of the silent electric discharge, asphalts,` and the like.

In general, the iiuoro derivatives may be prepared by treating the raw material with fluorine which may be conveniently obtained by electrolysis o f a metallic fluoride such as CaFa, KF', KFHF, and the like, or for example by methods such as those described in my U. S. Patent 2,090,772.

A method which may be used to advantage is shown in the drawing. Numeral l is a generator for the production of hydrogen fluoride, equipped with stirrer 2 and suitable means of heating.

These may be constructed of copper, iron coated.

with lead, resistant plastic, or other suitable corrosion resistant material. Sulfuric acid and calcium iiuoride used for the production of the hydrogen uoridemay be introduced into the generator at 3, and the sludge formed drawn o at 5, while hydrogen iiuoride vapor is led out at 4 directly to a scrubber 6, or through line 34 for indirect iluorination of chloro compounds as will be explained later. Scrubber 6, constructed of resistant metal or plastic is equipped with baffles or lplates, 1, upon which may be circulated a purifying solution such as a solution of turning sulfuric acid containing 210% potassium dichro- `fur dioxide and other impurities from the vapor. 'I'he solution is collected in corrosion resistant vessel l and circulated by pump l through line Il into chamber 8, and maybe replaced when exhausted. The puried HF issuing from line I2 is allowed to contact with an aqueous solution of KF or with solid finely ground KF entering the acidifier lll-at I4. By suitable countercurrent'contactor such as a screw conveyor or bame type of apparatus I3, the HF is caused to react with the KF to produce the 'double salt KFHF which is removed at i6. Any unused HF may be recirculatel by forcing it through line I1.

The double salt KF'HF (I9) is then electrolyzed ina copper electrolyzer i3 equipped with carbon electrodes` 20 and suitable insulating caps 2| made of iluorspar or the'like, and heated by some suitable means. It is preferable to keep the temperaturev at 200350 C. in the electrolyzer, so that by a current of -20 amperes at about volts.' areasonably steady stream of iluorine may be maintainedv at 22 and drawn off to storage throughline 35, or led directly into iluorinator 26. Hydrogen wi1l`be liberated'at 25, and may be collected in a suitable reservoir.

The pressure on both sides of the V of the electrolyzer must be kept at the same value as closely as is practical, since otherwise the iluorine or hydrogen would mix.

The fluorine so formed is led by pipe 22 into fluorinator 23 equipped with jacket 30 and inner coil 21 capable of cooling or heating the contents 33, while they are stirred with stirrer 32. The material to be fluorinated, such as mineral or vegetable oil, naphthalene, diphenyloxide, etc., is led into the vessel through 28 and reacted with the uorine dispersed through it by a spray forming arrangement 2B.

A suitable solvent or liquid reaction medium such as carbon tetrachloride, or the like may be introduced with the raw material in order to decrease the violence of the reaction. An inert gas or vapor such as nitrogen, carbon dioxide, and the like may also be introduced with the iluorine (fromV 10 to 90% of the total mixture) through line 36 to assist in the same manner. It is sometimes advantageous to introduce chlorine, hydrogen chloride, hydrogen iluoride or other halogen or halogen compounds with the fluorine. Any HF formed in the reaction may be bled of! at 3| and collected orv introduced at some point in line l such as 34 for recovery. In the case of veryreactive compounds such as naphthalene and many other organic compounds, it is necessary to lower the temperature of the fluorinator considerably to obtain the best results. Temperatures below 0 F.` as for instance 0 F., 70 F., or even lower'may be used. In such a case a slurry of solid naphthalene in carbon disulfide may be so treated. Fluorination catalysts, as for example bromine, antimony trichloride, antimony pentauoride, and the like, may likewise be present.

Another alternative method which may be employed with raw materials reactive with HF, as chlorinated organic compounds boiling above 400 F., unsaturated hydrocarbons, unsaturated glycerides, drying oils, oxygenated compounds, etc., is to lead the HF gas from 34 directly into the iluorinator 26 through line 35. 'Ihis is also a means of stabilizing unstable organic compounds. Heat may also be used, as for example temperatures of 40 F., 100 F., 200 F., 450 F. or even 500 F. with or without the use of supermate.' 'I'his mixture is well suited to remove sulatmospheric pressure. In such cases it is generally desirable to carry out the reaction Vin presence oi' a iluorination catalyst such as iodine. and the like, or a metal halide or metal iluoride as for example antimony penta or tri-chloride bismuth trichloride, boron triiluoride. etc. For example, chlorinated castor oil or chlorinated wax may be introduced into the fluorinator at 20, together with some antimony chloride (say l to 20% by weight), and reacted with HF entering at 22. A solvent such as kerosene. naphtha, white oil, or cyclohexane may be added with the charge. After the reaction has progressed to the desired stage, the products may be drawn of! at 31, or they may be drawn of! continuously while a continuous stream of raw material is i'ed in. In many cases it is not necessary to replace all 'of the chlorine in the material treated, and the resulting chloro-nuoro compound can be employed for a variety of purposes. products are suitable even when only very small quantitieso! tluorine are present.

The materials produced according to this invention may be employed as blending agents in lubricants, as for example as extreme pressure lubricants or fire resisting lubricants. and they may be used' as such, without diluents, for the preparation of lubricating oils, turbine oils. greases, and the like. For example, a blend oi' 5 to 50% or more of a nuoro compound in a mineral, synthetic or glyceride oil is satisfactory for reducing the inammability, while 0.01 to 5% of the Y, fiuoro or nuoro-chloro compound may be used as an oxidation or polymerization inhibitor, or as a blending agent to improve the oil in other respects.

The products, such as those containing between 5 to 60% fluorine or more, may also be employed as coatings, impregnating materials for fibrous substances as wood, cloth, and the like, as ingredients in paints, varnishes, lacquers and enamels. Due to their stabilityand combustion resistant properties, they serve as valuable compounding agents in rubber, asphalts, resins, reprooiing compounds, building materials, and the like, especially when they contain from 1 to 50% or even as high as 70% iluorine. They are valuable as blending agents in fuels, solvents, waxes,`

plastics, and other similar products, alone, or together with dyes, pigments, llers and compounding agents. They also serve as extraction agents forV improving the quality of light and heavy petroleum hydrocarbons, as precipitating agents, and as non-igniting oils for lubrication, insulation, for use in transformers, cables, condensers,

and other similar purposes, especially when they.

contain from approximately 10 to 60% fluorine. Plastic compositions containing 5 or 10 to 60% of such'fluorinated organic compounds are very lsuitable as moulding materials for various articles of furniture, equipment, etc. Resins may be fluorinated, especially when dissolved in solvents or admixed with other ingredients so as to contain 5 to 50% iluorine or even more. Various other materials such as paper, wood, cloth, leather, and the like may be treated with iluorine to improve the qualities thereof.

The nuoro compounds produced by the methods Sometimes the Theylmay 'also be reacted with materials of the u n 2,186,918 sodium polysuliide type to yield useful plastics l and oils. Numerous other condensation. polymerization, deuorination, and addition reactions may be carried out to produce useful products.

This invention is not limited to any of the specific examples or .by any particular'methods either of preparing or using the iluorinated materials, but only by the following claims in which it is my intention to cover the subject as broadly as the prior art permits.

I claim:

1. A lubricant comprising about 5 to about 60% of a iiuorinated aliphatic organic compound boiling about 400 F. 1

2. A non-igniting lubricant comprising a uorinated aliphatic organic compound boiling above 400 F. and containing from about 10 to about 60% uorine.

3. A lubricant comprising a mineral lubricating oil containing from 5 to about 50% of aliphatic iiuorinated compounds boiling above 400 F.

4. A lubricant comprising a mineral lubricating oil containing from to 50% oi aliphatic iluorinated hydrocarbon compounds boiling above A 5. A lubricant comprising a mineral lubricating v oil containing 0.01 to 5% of iluorinated aliphatic hydrocarbon compounds boiling above 400 F.

6. A mineral oil containing an amount of fluorinated aliphatic hydrocarbon compound boiling above 400 F. which represents 5 to 60% of iluorine in the blended lubricant.

PETER J.

A CERTIFICME oF CORRECTION. Patent ANo. 2,186,916. I yJanuary 9', 19140.

PETER J. WIIEZEVIICH, Y now. by judicial change of nameV PETER4 J. 'GAYLOILA I-t i hereby certified that error appears in the printed specification of the above numbered patent requiring correction. asl follows: Pge 5, firs-t column, line 114, claim l, for the word "gbout" read abore; that the said Letters Patent should be reed with this .correction therein that the same nay conform to the reco-rd of the ca se in the Patent Office. i I I signed and sealed this. 19th.daj of March, A.' D. 191m;

Henry Van Arsdale, (Sea 1) Acting .Commissioner of Patents. 

